TW201839111A - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal element, and polyorganosiloxane - Google Patents

Abstract

A silicon-containing compound having a cyclic ether group and a functional group B capable of reacting with a cyclic ether group is contained in a liquid crystal aligning agent. An example of the functional group B in the silicon-containing compound is a functional group capable of reacting with a cyclic ether group under heating. One example of the silicon-containing compound is a polymer [P] having a siloxane backbone.

Description

Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element, and polyorganosiloxane

The present disclosure relates to a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal element, and a polyorganosiloxane.

[Cross-Reference to Related Applications] This application is based on Japanese Application No. 2017-43288, filed on March 7, 2017, and the content described in this application is cited.

As the liquid crystal element, a type using a nematic liquid crystal having a positive dielectric anisotropy, typified by a Twisted Nematic (TN) type, a Super Twisted Nematic (STN) type, or the like is known. Liquid crystal elements, or vertical alignment (Vertical Alignment, VA) type liquid crystal elements using a homeotropic alignment mode with nematic liquid crystal with negative dielectric anisotropy, In-Plane Switching (IPS) Various types of liquid crystal elements, such as transverse electric field type liquid crystal elements, such as a Fringe Field Switching (FFS) type, are used to switch liquid crystals of homogeneous alignment using an electric field parallel to the substrate.

These liquid crystal elements include a liquid crystal alignment film having a function of aligning liquid crystal molecules in a certain direction. As materials used in the production of the liquid crystal alignment film, polyamic acid, polyimide, polyimide, polyester, polyorganosiloxane, and the like are known, and in particular polyamic acid and polyimide Since heat resistance, mechanical strength, and affinity with liquid crystal molecules are excellent, they have been preferably used since ancient times (for example, refer to Patent Documents 1 to 3). When manufacturing a liquid crystal element, a liquid crystal alignment film is formed using the liquid crystal alignment agent which melt | dissolved these polymer components in the organic solvent.

In addition, Patent Document 4 discloses a liquid crystal alignment agent containing a polyorganosiloxane obtained by reacting a mixture of trifunctional and tetrafunctional hydrolyzable silane compounds in the presence of oxalic acid and an alcohol. This Patent Document 4 describes that a liquid crystal alignment film formed of the liquid crystal alignment agent is excellent in vertical alignment and heat resistance.

Regarding liquid crystal elements, televisions, mobile phones, and tablet PCs have been the main markets in the past, but they have been widely used as display devices in recent years. As for liquid crystal elements, a wide range of new applications such as in-vehicle devices, digital signage, and industrial applications have been discovered, and they are used in a variety of applications. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 4-153622 [Patent Literature 2] Japanese Patent Laid-Open Publication No. 56-91277 [Patent Literature 3] Japanese Patent Laid-Open Publication No. 11-258605 [Patent Literature 4] Japanese Patent JP-A-9-281502

[Problems to be Solved by the Invention] With regard to new markets for liquid crystal elements, durability under severe use environments is sometimes required, and high reliability above the prior art is required. For example, when it is assumed to be used in a high temperature in summer or in a tropical area, heat resistance (thermal reliability) for a long time is required. On the other hand, for the display quality of the liquid crystal display panel, the contribution rate of the liquid crystal alignment film that is in direct contact with the liquid crystal layer is large. Therefore, as a liquid crystal alignment film, even when the liquid crystal display panel is exposed to a high temperature condition, it is required that the voltage holding ratio and the driving characteristics are not easily changed, and it is difficult to cause a reduction in display quality.

This disclosure is made in view of the said situation, and one of the objective is to provide the liquid crystal element which is excellent in the reliability with respect to heat. [Means for solving problems]

According to the present disclosure, the following means are provided.

<1> A liquid crystal alignment agent containing a silicon-containing compound having a cyclic ether group and a functional group B that reacts with the cyclic ether group. <2> A liquid crystal alignment film formed using the liquid crystal alignment agent as described in said <1>. <3> A liquid crystal element including the liquid crystal alignment film according to the above <2>. <4> A polyorganosiloxane having a cyclic ether group and a functional group B that reacts with the cyclic ether group. [Effect of the invention]

According to the liquid crystal alignment agent of the present disclosure, a liquid crystal element excellent in thermal reliability can be obtained.

<< Liquid crystal alignment agent >> The liquid crystal alignment agent of the present disclosure contains a silicon-containing compound (hereinafter, also referred to as "silicon-containing compound [A]") having a cyclic ether group and a functional group that reacts with the cyclic ether group. The silicon-containing compound [A] has a silicon-containing structure and a self-crosslinking group with high thermal stability. Hereinafter, each component contained in the liquid crystal aligning agent of this disclosure, and other components arbitrarily mix | blended as needed are demonstrated.

<Silicon-containing compound [A]> From the viewpoint of high reactivity due to heat, the cyclic ether group of the silicon-containing compound [A] is preferably an oxetanyl group or an oxiranyl group, More preferred is ethylene oxide. A functional group that reacts with a cyclic ether group (hereinafter, also referred to as "functional group B") in terms of self-crosslinking by heating at the time of post-baking and further improving the storage stability of the liquid crystal alignment agent. ) A functional group that reacts with a cyclic ether group by heat is preferred. Specific examples of the functional group B include, in addition to a carboxyl group, an isocyanate group, a hydroxyl group, an amine group, and an alkoxymethyl group, a group obtained by protecting a carboxyl group, an isocyanate group, a hydroxyl group, or an amine group with a protective group. In terms of better storage stability and higher reactivity with a cyclic ether group by heating, the functional group B is preferably a carboxyl group or a protected carboxyl group (hereinafter, also referred to as a "protected carboxyl group"). .

The protected carboxyl group is preferably one which is released by heat to generate a carboxyl group. Specific examples of the protected carboxyl group include a structure represented by the following formula (1), an acetal structure of a carboxylic acid, and a ketal structure of a carboxylic acid. [Chemical 1] (In formula (1), R ¹¹ , R ^12, and R ¹³ are each independently an alkyl group having 1 to 10 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or R ¹¹ and R ¹² are bonded to each other And together with the carbon atoms bonded by R ¹¹ and R ¹² to form a divalent alicyclic hydrocarbon group or cyclic ether group having 4 to 20 carbon atoms, and R ¹³ is an alkyl group having 1 to 10 carbon atoms and 2 to 10 carbon atoms Alkenyl group of 10 or aryl group having 6 to 20 carbon atoms. "*" Represents a bonding bond)

Examples of the silicon-containing compound [A] include a low-molecular-weight silane compound and a polyorganosiloxane. When the silicon-containing compound [A] is a low-molecular-weight silane compound, for example, an alkoxysilane compound having a cyclic ether group and a functional group B can be mentioned. In terms of obtaining a liquid crystal element having a higher improvement effect on thermal reliability and a liquid crystal alignment film having higher solvent resistance and better liquid crystal alignment and voltage retention, the silicon-containing compound [A] A polymer having a siloxane skeleton, that is, a polyorganosiloxane having a cyclic ether group and a functional group B (hereinafter, also referred to as "polymer [P]") is preferred.

<Polymer [P]> The method for synthesizing the polymer [P] is not particularly limited. As a preferable synthesis method, the following method 1 to method 3 can be cited. Method 1: Synthesis of a hydrolyzable silane compound (S1) having a cyclic ether group alone or a mixture of a silane compound (S1) and another hydrolyzable silane compound by hydrolysis and condensation to synthesize a Polyorganosiloxane (hereinafter, also referred to as "polyorganosiloxane E"), and then polyorganosiloxane E and carboxylic acid having an amine group (hereinafter, also referred to as "amino group-containing carboxylic acid" "), A method of obtaining a polyorganosiloxane having an amine group in a side chain, and further reacting the obtained polyorganosiloxane containing an amine group with a carboxylic acid anhydride. Method 2: Hydrolytic condensation of a mixture of a hydrolyzable silane compound (S2) and a silane compound (S1) having an amine group, or a mixture of a silane compound (S1) and a silane compound (S2) and other hydrolyzable silane compounds A polyorganosiloxane having an amine group and a cyclic ether group in a side chain (hereinafter, also referred to as "polyorganosiloxane M") is synthesized, and then the obtained polyorganosiloxane M is reacted with a carboxylic acid anhydride. Methods. · Method 3: The polyorganosiloxane E is synthesized by hydrolyzing and condensing the silane compound (S1) alone or a mixture of the silane compound (S1) and other hydrolyzable silane compounds, and then the polyorganosiloxane E and Method for reacting amine-containing carboxylic acids. Among these, the method 1 is preferably used because a polymer having high solubility in solvents and high heat resistance can be obtained easily.

As the silane compound (S1), a hydrolyzable silane compound having an oxetanyl group or an ethylene oxide group can be preferably used. Specific examples thereof include glycidyloxymethyltrimethoxysilane, glycidyloxymethyltriethoxysilane, 2-glycidyloxyethyltrimethoxysilane, and 2-glycidyloxy Ethylethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxy Silane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, (3-ethyloxetane-3-yl) methacrylate, (methyl) Acrylic (3-methyloxetane-3-yl) methyl and the like. The silane compound (S1) may be used alone or in combination of two or more.

As the silane compound (S2), a hydrolyzable silane compound having a primary amine group or a secondary amine group can be preferably used. Specific examples thereof include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, and 2-aminopropyltrimethoxysilane. Ethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxy Silane, N-phenyl-3-aminopropyltrimethoxysilane and the like. The silane compound (S2) may be used alone or in combination of two or more.

The other silane compounds are silane compounds other than the silane compound (S1) and the silane compound (S2), and are not particularly limited, and examples thereof include tetraalkoxysilane compounds such as tetramethoxysilane and tetraethoxysilane; methyl groups; Alkyl or aryl-containing alkoxysilane compounds such as triethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and dimethyldiethoxysilane; 3-mercaptopropyltriethyl Sulfur-containing alkoxysilane compounds such as oxysilane, mercaptomethyltriethoxysilane; 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyl Unsaturated alkoxysilane compounds such as methylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, vinyltriethoxysilane; trimethoxy Alkoxysilane compounds containing acid anhydride groups such as silylpropyl succinic anhydride; N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, 3-fluorenylpropyltrimethoxysilane, 3-氮 Ureapropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylene) propylamine, and other nitrogen-containing alkane Oxysilane compounds, etc. As other silane compounds, one kind of these may be used alone, or two or more kinds may be used in combination.

Examples of the amino group-containing carboxylic acid include 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminocyclohexanecarboxylic acid, 3-aminocyclohexanecarboxylic acid, and 6-amino group. 2-naphthoic acid, β-alanine, glycine, 3-aminocyclopentanecarboxylic acid, 5-aminopentanoic acid, 4-aminohydrocinnamic acid, 4-aminophenylacetic acid, 4- (Aminomethyl) benzoic acid and the like. As for the amine group-containing carboxylic acid, one of these may be used alone, or two or more of them may be used in combination.

The carboxylic acid anhydride may have only one acid anhydride group, and the remaining structure is not particularly limited. Examples of the carboxylic acid anhydride include trimellitic anhydride, 4-nitrophthalic anhydride, 3-nitrophthalic anhydride, 4-ethynylphthalic anhydride, and 4- (1-propyne Phthalic anhydride, 4-phenylethynyl phthalic anhydride, 4-methyl phthalic anhydride, phthalic anhydride, maleic anhydride, succinic anhydride, itaconic anhydride, allyl Succinic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 1-cyclohexene-1,2-dicarboxylic anhydride, cis-4-cyclohexene-1,2-dicarboxylic anhydride, 5-nor Borneene-2,3-dicarboxylic anhydride, Homophthalic acid anhydride, glutaric anhydride, 3-trimethoxysilylpropylsuccinic anhydride, cyclohexane-1,2,4-tricarboxylic acid Acid-1,2-anhydride and the like. As for the carboxylic acid anhydride, one kind of these may be used alone, or two or more kinds may be used in combination.

(Hydrolytic condensation reaction) In methods 1 to 3, the hydrolysis and condensation reaction using a hydrolyzable silane compound is performed as described above. One or two or more hydrolyzable silane compounds are preferably used with water as an appropriate catalyst and organic. The reaction proceeds in the presence of a solvent. In the methods 1 and 3, the use ratio of the silane compound (S1) is preferably 5 mol% or more, more preferably 10 mol% or more, relative to the total amount of the monomers used in the synthesis of the polyorganosiloxane. . In addition, in the method 2, the use ratio of the silane compound (S1) is preferably 5 mol% to 99 mol% with respect to the total amount of the monomers used in the synthesis of the polyorganosiloxane, and more preferably It is set to 10 mol% to 95 mol%. The use ratio of the silane compound (S2) is preferably 0.5 mol% to 50 mol%, and more preferably 1 mol% relative to the total amount of the monomers used in the synthesis of the polyorganosiloxane. ~ 40 mole%.

In the hydrolysis and condensation reaction, the use ratio of water is preferably 1 to 30 mols relative to 1 mol of the silane compound (total amount) used in the reaction. Examples of the catalyst used include acids, alkali metal compounds, organic bases, titanium compounds, zirconium compounds, and the like. Among them, tertiary organic amines or quaternary organic amines are preferred, and examples thereof include triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, and the like. Tertiary organic amines; tertiary organic amines such as tetramethylammonium hydroxide. The amount of the catalyst used should be appropriately set depending on the type of the catalyst, the reaction conditions such as temperature, etc., and should be appropriately set. For example, it is preferably 0.01 to 3 times mole relative to the total amount of the silane compound.

Examples of the organic solvent used in the hydrolysis and condensation reaction include hydrocarbons, ketones, esters, ethers, and alcohols. Examples of such hydrocarbons include toluene and xylene; and ketones include methyl ethyl ketone, methyl isobutyl ketone, methyl-n-pentyl ketone, diethyl ketone, and cyclohexanone. Examples of the ester include ethyl acetate, butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and ethyl lactate; examples of the ether include ethylene glycol Dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, and the like; examples of the alcohol include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether. Among these, it is preferable to use a water-insoluble or poorly water-soluble organic solvent. The use ratio of the organic solvent is preferably 10 parts by mass to 10,000 parts by mass with respect to 100 parts by mass of the total of the silane compound used in the reaction.

The hydrolysis condensation reaction is preferably carried out by heating with an oil bath or the like, for example. In this case, the heating temperature is preferably 130 ° C. or lower, and the heating time is preferably 0.5 to 12 hours. After the reaction is completed, the organic solvent layer separated from the reaction liquid is dried with a desiccant as necessary, and the solvent is removed to obtain a target polyorganosiloxane. The method for synthesizing the polyorganosiloxane is not limited to the hydrolysis and condensation reaction. For example, the method may be performed by a method of reacting a hydrolyzable silane compound in the presence of oxalic acid and an alcohol.

(Reaction of polyorganosiloxane E with amine-containing carboxylic acid (1)) In method 1, the cyclic ether group of organosiloxane E and the carboxyl group of amine-containing carboxylic acid are reacted, and Obtained from a polyorganosiloxane having an amine group in a side chain. The reaction is preferably performed in the presence of a suitable catalyst and an organic solvent.

As the catalyst used in the reaction, for example, in addition to an organic base that can be preferably used, a hardening accelerator can be used. As specific examples of these, examples of the organic base include primary organic amines or secondary organic amines, tertiary organic amines, and quaternary organic amine salts. Examples of the hardening accelerator include tertiary amines, imidazole derivatives, and organic phosphorus compounds. , Quaternary phosphonium salts, diazabicyclic olefins, organometallic compounds, quaternary ammonium halides, metal halides, potential hardening accelerators, etc. As the latent hardening accelerator, for example, a high melting point dispersive latent hardening accelerator (such as an amine addition molding accelerator), a microcapsule latent latent hardening accelerator, an amine salt latent hardening accelerator, and a high temperature can be listed. Dissociation type thermal cationic polymerization type latent hardening accelerator, etc. As a catalyst, it is preferable to use a quaternary organic amine salt or a quaternary ammonium halide among these.

Specific examples of the catalyst include tetramethylammonium hydroxide and the like; for example, tetramethylammonium hydroxide; and tetraethylammonium bromide, tetra-n-butylammonium bromide, and chloride Tetraethylammonium, tetra-n-butylammonium chloride, etc. As the catalyst, one or more selected from these may be used. The use ratio of the catalyst is preferably 0.01 to 100 parts by mass, and more preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the polyorganosiloxane E.

Examples of the organic solvent used in the reaction between the polyorganosiloxane E and the carboxylic acid include ketones, ethers, esters, amidines, and alcohols. As specific examples of the organic solvent, examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl-n-pentyl ketone, diethyl ketone, and cyclohexanone; and the ether such as Examples include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, and dioxane. Examples of the ester include ethyl acetate, n-butyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, and the like. 3-methoxybutyl acetate, ethyl lactate, and the like; examples of the amide include formamide, N-methylformamide, N, N-dimethylformamide, and N-ethyl Formamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide, N, N- Diethylacetamidamine, N-methylpropanamine, N-methylpyrrolidone, N-formylmorpholine, N-formylpiperidine, N-formylpyrrolidine, N-ethyl Fluorenylmorpholine, N-acetylfluorinated piperidine, N-acetylfluorinated pyrrolidine and the like; examples of the alcohol include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol Glycol mono - n-propyl ether and the like, can be selected using one or more of the plurality. The use ratio of the organic solvent is preferably a ratio of the total mass of components other than the organic solvent in the reaction solution to the total amount of the reaction solution to be 0.1% to 50% by mass, and more preferably set to be 5 to 50% by mass.

The use ratio of the amine group-containing carboxylic acid is appropriately set according to the number of the functional groups B introduced into the side chain of the polyorganosiloxane E, but the heat and reliability of the liquid crystal element caused by the introduction of the functional groups B are sufficiently obtained. From the viewpoint of the effect of improving the properties and the solvent resistance of the liquid crystal alignment film, it is preferably set to 0.005 mol to 0.5 mol relative to 1 mol of the silane compound (total amount) used in the synthesis of the polyorganosiloxane. ear. The lower limit of the use ratio is more preferably 0.01 mol or more, and still more preferably 0.05 mol or more. The upper limit value is more preferably 0.4 mol or less, and further preferably 0.3 mol or less.

In the method 1, when a polyorganosiloxane E is reacted with an amine-containing carboxylic acid, a functional group (hereinafter, also referred to as a "function" For the purpose, a carboxylic acid having a functional group (hereinafter, also referred to as a "functional group-containing carboxylic acid") may be used in combination. In the case of using a functional group-containing carboxylic acid together with an amine-containing carboxylic acid, in order to introduce a sufficient amount of a functional group without suppressing the introduction of the amine group, it is preferable to use a functional group-containing carboxylic acid. The total use ratio is 0.05 mol to 0.8 mol, and more preferably 0.1 mol to 0.7 mol, based on 1 mol of the silane compound (total amount) used in the synthesis of the polyorganosiloxane.

The reaction between the polyorganosiloxane E and the amine-containing carboxylic acid is performed at a temperature of preferably 0 ° C to 200 ° C, more preferably 50 ° C to 150 ° C, preferably 0.1 to 50 hours, and more preferably 0.5. Hours to 20 hours. After the reaction is completed, if necessary, the organic solvent layer separated from the reaction solution is dried with a desiccant, and then the solvent is removed to obtain an amine group-containing polyorganosiloxane.

(Reaction of amine group-containing polyorganosiloxane with carboxylic anhydride) In method 1 and method 2, the amine group of the polyorganosiloxane and the acid anhydride group of the carboxylic acid anhydride are reacted. Thereby, as the polymer [P], a polyorganosiloxane having an epoxy group and a carboxyl group in a side chain can be obtained.

From the viewpoint of sufficiently obtaining the thermal reliability of the liquid crystal element and the effect of improving the solvent resistance of the liquid crystal alignment film by the introduction of the functional group B (here, the carboxyl group) toward the polyorganosiloxane group, The use ratio of the carboxylic acid anhydride is preferably 0.1 mol to 2.0 mol with respect to 1 mol (total amount) of the amine group of the polyorganosiloxane. The lower limit of the use ratio is more preferably 0.2 mol or more, and even more preferably 0.3 mol or more. The upper limit value is more preferably 1.5 mol or less, and even more preferably 1.2 mol or less.

The reaction is preferably performed in a suitable organic solvent. Examples of the organic solvent used include aprotic polar solvents, phenol-based solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. Preferred organic solvents include those selected from the group consisting of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfinium, One or more of the group consisting of γ-butyrolactone, tetramethylurea, hexamethylphosphonium triamine, m-cresol, xylenol and halogenated phenol.

In the reaction, the reaction temperature is preferably -20 ° C to 100 ° C, and more preferably 0 ° C to 80 ° C. The reaction time is preferably 1 hour to 48 hours, and more preferably 2 hours to 12 hours. The obtained reaction solution may be directly used for the preparation of the liquid crystal alignment agent, or the polymer [P] contained in the reaction solution may be isolated and used for the preparation of the liquid crystal alignment agent by using a known isolation method.

(Reaction between polyorganosiloxane E and amine-containing carboxylic acid (2)) In method 3, the cyclic ether group of polyorganosiloxane E and the amine of amine-containing carboxylic acid基 反应。 Base reaction. Thereby, as the polymer [P], a polyorganosiloxane having an epoxy group and a carboxyl group in a side chain can be obtained.

Use of an amine group-containing carboxylic acid from the viewpoint of sufficiently obtaining the thermal reliability of a liquid crystal element and the improvement effect of the solvent resistance of a liquid crystal alignment film by the introduction of a carboxyl group toward a side chain of a polyorganosiloxane. The ratio is preferably 0.005 mol to 0.5 mol relative to 1 mol of the silane compound (total amount) used in the synthesis of the polyorganosiloxane. The lower limit of the use ratio is more preferably 0.01 mol or more, and still more preferably 0.05 mol or more. The upper limit value is more preferably 0.4 mol or less, and even more preferably 0.3 mol or less.

The reaction is performed in the presence of a suitable catalyst in a suitable solvent, if necessary. Examples of the catalyst include magnesium oxide, calcium oxide, and potassium carbonate. The solvent is preferably one capable of uniformly dissolving or decomposing an amine-group-containing polyorganosiloxane and a carboxylic anhydride, and examples thereof include N-methyl-2-pyrrolidone and tetrahydrofuran. In the reaction, the reaction temperature is preferably -20 ° C to 180 ° C, and more preferably 10 ° C to 120 ° C. The reaction time is preferably 1 hour to 72 hours, and more preferably 2 hours to 48 hours. The obtained reaction solution can be used to prepare a liquid crystal alignment agent after the polymer [P] contained in the reaction solution is isolated by a known isolation method.

In the method 2 and the method 3, in the case where a polyorganosiloxane having a functional group is used as the polymer [P], the method 2 may be performed before the polyorganosiloxane having an amine group is reacted with a carboxylic acid anhydride. A polyorganosiloxane having a cyclic ether group is reacted with a functional group-containing carboxylic acid. As for the method 3, a polyorganosiloxane having a cyclic ether group can be reacted before the polyorganosiloxane is reacted with an amine-containing carboxylic acid. Polyorganosiloxanes react with carboxylic acids containing functional groups. Regarding the reaction conditions of a polyorganosiloxane having a cyclic ether group and a carboxylic acid having a functional group, the description of the method 1 is applied.

An example of the methods 1 to 3 is shown in the following flow A1, flow A2, flow B, and flow C. In the method 1, when an epoxy-containing silane compound is used as the silane compound (S1), 3-aminobenzoic acid is used as the amine-containing carboxylic acid, and trimellitic anhydride is used as the carboxylic acid anhydride, The polymer [P] is obtained by the following scheme A1 (beta cracking of an epoxy group) and scheme A2 (alpha cracking of an epoxy group). [Chemical 2] [Chemical 3] (In Schemes A1 and A2, L ¹ is a divalent linking group, and R ¹ is a hydrogen atom)

In the method 2, when an epoxy group-containing silane compound is used as the silane compound (S1) and trimellitic anhydride is used as the carboxylic acid anhydride, a polymer [P] can be obtained by the following scheme B. [Chemical 4] (In process B, L ¹ and L ² are each independently a divalent linking group)

In the method 3, when an epoxy-containing silane compound is used as the silane compound (S1) and 4-aminobenzoic acid is used as the amine-containing carboxylic acid, a polymer can be obtained by the following scheme C [ P]. [Chemical 5] (In Scheme C, L ¹ is a divalent linking group, and R ³ is a hydrogen atom)

According to the processes A1, A2, and B, as the polymer [P], a polyorganosiloxane having a cyclic ether group (here, ethylene oxide group) and a carboxyl group, and a cyclic ether can be obtained. And amine-based polyorganosiloxanes. In addition, according to the scheme C, as the polymer [P], a polyorganosiloxane having a cyclic ether group and a carboxyl group can be obtained.

(Functional Group) The polymer [P] preferably has a functional group in the side chain according to the driving mode of the liquid crystal element to be applied. For example, when a liquid crystal alignment agent is used in the manufacture of a liquid crystal element of a vertical alignment type or a horizontal alignment type, the polymer [P] preferably has an alignment manifestation site that aligns liquid crystal molecules as a functional group. In addition, in the case where a polymer film formed of a liquid crystal alignment agent is provided with liquid crystal alignment energy by a photo alignment method, the polymer [P] preferably has a photo alignment group as a functional group. In addition, in the case where the alignment limiting force of liquid crystal molecules is increased by irradiating light from the outside of the liquid crystal cell after the construction of the liquid crystal cell, the polymer [P] preferably has a group containing a carbon-carbon unsaturated bond as Functional base.

[Alignment Appearance Site] The orientation display site is a group that can control the alignment direction of liquid crystal molecules in a liquid crystal layer for a polymer film formed using a liquid crystal alignment agent. In addition, the alignment display site can control the alignment of liquid crystal molecules without light irradiation. As a specific example of an orientation display part, the group etc. which are represented by following formula (3) are mentioned, for example. [Chemical 6] (In formula (3), R ^I is an alkyl group having 1 to 40 carbon atoms, a fluoroalkyl group having 1 to 40 carbon atoms, and at least one hydrogen atom of an alkyl group having 1 to 40 carbon atoms is substituted with a cyano group. Valence group, cyano group, nitro or fluorine atom, or a hydrocarbon group having 17 to 51 carbon atoms having a steroid skeleton. Z ^I is a single bond, * -O-, * -COO- or * -OCO- (wherein, The "*" bond is on the R ^I side). R ^II is cyclohexyl or phenyl, and the hydrogen atom bonded to the ring can also pass through a cyano, nitro, fluorine atom, trifluoromethyl or carbon number 1 ~ 3 alkyl substitution. When n1 is 1 or 2, when n1 is 2, the two R ^II may be the same as or different from each other. N 2 is 0 or 1. Z ^II is a single bond, * -O-, * -COO -Or * -OCO- (where the bond with "*" is on the R ^II side). N3 is an integer from 0 to 2 and n4 is 0 or 1. In the case of n2 = 0 and n4 = 0 , R ^I is 4 or more carbon atoms)

Examples of the divalent group represented by "-(R ^II ) _n1- " in the formula (3) include 1,4-phenylene, 1,4-cyclohexyl, and 4,4'-phenylene. Phenyl, 4,4'-bicyclohexyl, the following formula [Chem. 7] (In the formula, a bond with "*" is attached to the Z ^I bond.) The bases and the like respectively indicated are preferred divalent bases.

[Photo-alignable group] The photo-alignable group is a functional group that imparts anisotropy to a film by a photo-isomerization reaction or a photo-dimerization reaction, a photo-decomposition reaction, and a photo-Fries rearrangement reaction caused by light irradiation. Specific examples of the photo-alignment group include an azobenzene-containing group containing azobenzene or a derivative thereof as a basic skeleton, and a cinnamic acid containing cinnamic acid or a derivative thereof (cinnamic acid structure) as a basic skeleton. Structural group, chalcone-containing group containing chalcone or its derivative as a basic skeleton, benzophenone-containing group containing benzophenone or its derivative as a basic skeleton, coumarin or its A coumarin-containing group having a basic skeleton as a derivative, a cyclobutane-containing structure including cyclobutane or a derivative thereof as a basic skeleton, and the like. In terms of high sensitivity to light or easy introduction into a polymer side chain, a group having a cinnamic acid structure represented by the following formula (5) is preferred. The polymer [P] is preferable in that it can improve the high-speed responsiveness of the obtained liquid crystal element by having a pretilt angle developing portion together with the structure represented by the following formula (5). [Chemical 8] (In formula (5), R is a fluorine atom or a cyano group. A 'is an integer of 0 to 4. When a' is 2 or more, a plurality of R may be the same or different. "*" Represents a bonding bond)

[Group containing carbon-carbon unsaturated bond] Examples of the group containing a carbon-carbon unsaturated bond include a group represented by the following formula (4). [Chemical 9] (In formula (4), R is a hydrogen atom or a methyl group, X ^I and X ^II are 1,4-phenylene, an alkyldiyl group having 1 to 8 carbon atoms, and Z is an oxygen atom, -COO- * or -OCO- * (where the bond with "*" is bonded to X ^II ), a, b, c, and d are 0 or 1. Where c is 0 and d is 1, X ^II is 1,4-phenylene, c is 0 when b is 0)

Specific examples of the group represented by the formula (4) include a vinyl group, an allyl group, a p-vinylphenyl group, a (meth) acryloxyoxyalkyl group, and 4-((methyl) group. Acrylic alkoxy) alkyl) phenyl, ((meth) acrylic ethoxy) phenyl) alkyl, 4-((meth) acrylic ethoxyalkoxy) phenyl, (meth) acrylic Alkoxyalkoxyalkyl, 6-[[6- (propenyloxy) hexyl] oxy} hexyl, and the like.

When the polymer [P] is a polymer having a functional group in a side chain, the polymer can be exemplified by (I) a method synthesized by polymerization of a monomer having a functional group, and (II) A method for introducing a cyclic ether group in a polymer [P] or a precursor thereof into a side chain, and the like. Among these, (II) is preferable in terms of simple and easy adjustment of the introduction rate of the functional group. Among them, it is preferable to use a polyorganosiloxane having a cyclic ether group (polyorganosiloxane E in method 1 and method 3, polyorganosiloxane M in method 2), and a functional group B and a functional group compound (hereinafter, also referred to as "side chain precursor [C]") are produced by reaction.

In addition, the polymer [P] may have only one of an alignment manifestation site, a photo-alignment group, and a group containing a carbon-carbon unsaturated bond as a functional group, or may have a plurality of types. In the case where the polymer [P] has a plurality of the functional groups, one functional group and other functional groups may exist in the same side chain, or may exist in different side chains. In addition, all of the functional groups may be contained in a single type of polymer, or may be used as a mixture of a polymer having a part of a desired functional group and a polymer having a remaining functional group. Of course, three or more polymers may be mixed and used as the polymer [P], and two or more polymers having the same functional group may be mixed and used. The polymer [P] may have any functional group as a single substance or a mixture as a whole, since it can be in any state.

The polymer [P] has a polystyrene-equivalent weight average molecular weight (Mw) measured by Gel Permeation Chromatography (GPC) of preferably 1,000 to 300,000, more preferably 2,000 to 100,000. Among them, when the polymer [P] is a modified polymer modified using a compound having a functional group, it is preferable that the weight-average molecular weight of the polymer before the modification is within the above range. The molecular weight distribution (Mw / Mn) represented by the ratio of Mw to the polystyrene-equivalent number average molecular weight (Mn) measured by GPC is preferably 5 or less, and more preferably 4 or less. In addition, the polymer [P] used in the preparation of the liquid crystal alignment agent may be only one kind, or two or more kinds may be combined.

From the viewpoint that the effect of improving the thermal reliability of the obtained liquid crystal element can be sufficiently obtained, the content ratio of the polymer [P] in the liquid crystal alignment agent is larger than 100 parts by mass of all the polymers contained in the liquid crystal alignment agent. It is preferably at least 0.1 parts by mass, more preferably at least 0.5 parts by mass, and even more preferably at least 1 part by mass. In the case of blending other polymers, the content of the polymer [P] is preferably 50 parts by mass or less, and more preferably 25 parts by mass or less, relative to 100 parts by mass of the other polymers contained in the liquid crystal alignment agent. It is further preferably 20 parts by mass or less.

<Other Components> The liquid crystal alignment agent of the present disclosure contains the polymer [P] as described above, but may optionally contain other components shown below.

(Other polymers) The liquid crystal alignment agent of the present disclosure may contain a polymer different from the polymer [P] in order to obtain various performance improvement effects such as electrical characteristics, liquid crystal alignment, and reliability, or to reduce costs. (Hereinafter, also referred to as "other polymers"). The main skeleton of other polymers is not particularly limited. Examples of the other polymers include polyamic acid, polyimide, polyamidate, polyamidamine, polyorganosiloxane other than polymer [P], polyester, cellulose derivative, Polymers having a main skeleton such as polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, and poly (meth) acrylate. In addition, in this specification, "(meth) acrylate" means including an acrylate and a methacrylate.

From the viewpoints of electrical characteristics, affinity with liquid crystals, mechanical strength, affinity with polymers [P], etc., other polymers are preferably those selected from the group consisting of polyamic acid and polyamic acid esters. At least one polymer (hereinafter, also referred to as "polymer [Q]") in the group consisting of a polymer of polyimide and a monomer having a polymerizable unsaturated bond. The blending ratio of the polymer [Q] is preferably 100 parts by mass or more, more preferably 100 to 2000 parts by mass, relative to 100 parts by mass of the polymer [P] used in the preparation of the liquid crystal alignment agent. Furthermore, it is more preferable that it is 200 mass parts-1500 mass parts.

(Polyamidate, Polyamidate, and Polyimide) The polyamidate, polyamidate, and polyimide contained in the liquid crystal alignment agent can be synthesized according to a conventionally known method. For example, polyamic acid can be obtained by reacting a tetracarboxylic dianhydride with a diamine. The polyamidate can be obtained, for example, by a method of reacting polyamidate with an esterifying agent (for example, methanol, ethanol, N, N-dimethylformamide diethyl acetal, and the like). Polyfluorene imine can be obtained, for example, by dehydrating and ring-closing polyphosphonium acid and performing fluorimidination. In addition, the polyfluorene imine preferably has a hydrazone imidization rate of 20% to 95%, and more preferably 30% to 90%. The fluorene imidization ratio is a percentage expressed as a percentage of the number of fluorene imine ring structures relative to the sum of the number of fluorene acid structures of polyfluorene and the number of fluorene imine rings.

Examples of the tetracarboxylic acid used in the polymerization include aliphatic tetracarboxylic dianhydrides such as butane tetracarboxylic dianhydride and ethylenediamine tetraacetic dianhydride; 1,2,3,4-cyclobutane tetracarboxylic acid Acid dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 5- (2,5 -Dioxotetrahydrofuran-3-yl) -3a, 4,5,9b-tetrahydronaphthalene [1,2-c] furan-1,3-dione, 5- (2,5-dioxotetrahydrofuran- 3-yl) -8-methyl-3a, 4,5,9b-tetrahydronaphthalene [1,2-c] furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo [3.3 .0] alicyclic tetracarboxylic dianhydride such as octane-2: 4,6: 8-dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride; pyromellitic dianhydride 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride, p-phenylene bis (trimellitic acid monoester anhydride), ethylene glycol bis (trimellitic anhydride), 1,3-propanediol bis In addition to an aromatic tetracarboxylic dianhydride such as (trimellitic anhydride), the tetracarboxylic dianhydride described in Japanese Patent Laid-Open No. 2010-97188 can be used. Moreover, tetracarboxylic dianhydride may be used individually by 1 type, and may use 2 or more types together.

Examples of the diamine used in the polymerization include aliphatic diamines such as ethylenediamine and tetramethylenediamine; p-cyclohexanediamine and 4,4'-methylenebis (cyclo Hexylamine) and other alicyclic diamines; hexadecyloxydiaminobenzene, cholesteryloxydiaminobenzene, cholesteryl diaminobenzoate, cholesterolyl diaminobenzoate, Lanosteryl diaminobenzoate, 3,6-bis (4-aminobenzyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 2,5-diamino-N, N-diallylaniline, the following Formulas (8-1) to (8-3)

Compounds represented by the side chain type aromatic diamines, etc .; p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylamine, 4-amino group Phenyl-4'-aminobenzoate, 4,4'-diaminoazobenzene, 3,5-diaminobenzoic acid, 1,5-bis (4-aminophenoxy) pentyl Alkane, bis [2- (4-aminophenyl) ethyl] adipic acid, bis (4-aminophenyl) amine, N, N-bis (4-aminophenyl) methylamine, N , N'-bis (4-aminophenyl) -benzidine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 4, 4 '-(phenylene diisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4- (4-aminophenoxycarbonyl) -1- (4- Non-side chain aromatics such as aminophenyl) piperidine, 4,4 '-[4,4'-propane-1,3-diylbis (piperidine-1,4-diyl)] diphenylamine Diamine; diamine organosiloxanes such as 1,3-bis (3-aminopropyl) -tetramethyldisilazane, etc. can be used in Japanese Patent Laid-Open No. 2010-97188 Documented diamine. Moreover, a diamine may be used individually by 1 type, and may use 2 or more types together.

Regarding the polyamidic acid, polyamidate, and polyimide contained in the liquid crystal alignment agent, the polystyrene-equivalent weight average molecular weight (Mw) measured by GPC is preferably 1,000 to 500,000, and more preferably 2,000. ~ 300,000. The molecular weight distribution (Mw / Mn) is preferably 7 or less, and more preferably 5 or less. In addition, the polyamidic acid, polyamidate, and polyimide contained in the liquid crystal alignment agent may be only one kind, or two or more kinds may be combined.

(Polymer of polymerizable unsaturated bond monomer) A polymer of a polymerizable unsaturated bond monomer (hereinafter, also referred to as "polymer PAc") is included as a monomer constituting the polymer PAc. Examples of the polymerizable unsaturated bond include (meth) acrylfluorenyl, vinyl, styryl, and maleimido. Specific examples of the monomer having these polymerizable unsaturated bonds include (meth) acrylic compounds such as unsaturated carboxylic acid, unsaturated carboxylic acid ester, and unsaturated polycarboxylic acid anhydride; styrene, methyl Aromatic vinyl compounds such as styrene and divinylbenzene; conjugated diene compounds such as 1,3-butadiene and 2-methyl-1,3-butadiene; N-methylmaleimide , Maleimide compounds such as N-cyclohexylmaleimide, N-phenylmaleimide and the like. The monomer having a polymerizable group unsaturated bond may be used alone or in combination of two or more.

The polymer PAc is preferably a poly (meth) acrylate. The poly (meth) acrylate may be a polymer containing only a (meth) acrylic compound, or may be a polymer containing a (meth) acrylic compound and other monomers. Examples of the other monomer include a conjugated diene compound, an aromatic vinyl compound, and a maleimide compound. The poly (meth) acrylate preferably has a structural unit derived from a (meth) acrylic compound in an amount of 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, particularly preferably 70% by mass or more.

The (meth) acrylic compound used in the polymerization is not particularly limited. Specific examples of the unsaturated carboxylic acid include (meth) acrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, and itaconic acid. Examples of the unsaturated carboxylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and (formaldehyde). Allyl acrylate, cyclohexyl (meth) acrylate, tricyclic [5.2.1.0 ^2,6 ] dec-8-yl, dicyclopentyl (meth) acrylate, (formyl) (Benzyl) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, trimethoxysilylpropyl (meth) acrylate, 2,2,2 -Trifluoroethyl, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, methoxyethyl (meth) acrylate, -N, N-dimethyl (meth) acrylate Aminoethyl ester, methoxypolyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, (formyl) Propyl) 3,4-epoxycyclohexyl methyl acrylate, (meth) propyl 3,4-epoxybutyl acid, 4-hydroxybutyl glycidyl acrylate, etc .; Examples of unsaturated polycarboxylic acid anhydrides include maleic anhydride, itaconic anhydride, cis-1,2,3,4-tetra Hydrophthalic anhydride and so on. The (meth) acrylic compounds may be used alone or in combination of two or more.

The polymerization reaction using a (meth) acrylic compound is preferably performed by radical polymerization. As the polymerization initiator used in the polymerization reaction, for example, 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylpentane) can be preferably used. Nitriles), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) and other azo compounds. The use ratio of the polymerization initiator is preferably 0.01 to 40 parts by mass with respect to 100 parts by mass of the total of the monomers used in the reaction.

The polymerization reaction of the (meth) acrylic compound is preferably performed in an organic solvent. Examples of the organic solvent used in this reaction include alcohols, ethers, ketones, amidines, esters, and hydrocarbon compounds. Among these, it is preferable to use at least one selected from the group consisting of an alcohol and an ether, and it is more preferable to use a partial ether of a polyhydric alcohol. Preferred examples thereof include diethylene glycol methyl ether and propylene glycol monomethyl ether acetate. In addition, these organic solvents may be used alone or in combination of two or more thereof.

In the polymerization reaction of the (meth) acrylic compound, the reaction temperature is preferably 30 ° C. to 120 ° C., and the reaction time is preferably 1 hour to 36 hours. The amount (a) of the organic solvent is preferably an amount in which the total amount (b) of the monomers used in the reaction is 0.1% by mass to 50% by mass with respect to the total amount (a + b) of the reaction solution. The polystyrene-equivalent number average molecular weight (Mn) obtained by measuring poly (meth) acrylate by GPC is preferably 250 to 500,000, more preferably 500 to 100,000, and even more preferably 1,000 to 50,000.

As other components, for example, a compound having at least one epoxy group in the molecule (except for compounds corresponding to the silicon-containing compound [A]) and a functional silane compound (except for equivalent to Silicon-containing compound [A] compound), antioxidant, metal chelate compound, hardening accelerator, cross-linking agent, surfactant, filler, dispersant, light sensitizer, etc. The blending ratio of other components may be appropriately selected depending on each compound within a range that does not impair the effects of the present disclosure.

(Solvent) The liquid crystal alignment agent of the present disclosure is prepared as a solution-like composition obtained by dissolving or dispersing a polymer component and a component arbitrarily arbitrarily optionally in an organic solvent. Examples of the organic solvent used include aprotic polar solvents, phenol-based solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. The solvent component may be one of these or a mixed solvent of two or more.

Specific examples of the organic solvent used include, for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1,2-dimethyl-2-imidazolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethyl Glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol-n-propyl ether , Ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethylene glycol Diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate , Isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene carbonate, cyclohexane, octanol, tetrahydrofuran and the like. In addition, the hydrocarbon solvent containing no fluorene imine structure may be used for the purpose of application to a plastic substrate or low-temperature firing.

As the solvent component, it is preferable to use at least one selected from the group consisting of compounds represented by the following formulae (E-1) to (E-5) and having a boiling point of 180 ° or less at 1 atmosphere. Solvents (hereinafter also referred to as "specific solvents"). These specific solvents can provide good coatability (printability) of the liquid crystal alignment agent and obtain excellent liquid crystal alignment and electrical characteristics even when the film is heated at a low temperature (for example, 200 ° C. or lower) during film formation. A liquid crystal element is preferable. [Chemical 11] (In the formula (E-1), R ⁴¹ is an alkyl group having 1 to 4 carbon atoms or CH ₃ CO-, and R ⁴² is an alkyl dialkyl group having 1 to 4 carbon atoms or-(R ⁴⁷ -O) rR ^48- ( Among them, R ⁴⁷ and R ⁴⁸ are each independently an alkanediyl group having 2 or 3 carbon atoms, r is an integer of 1 to 4), and R ⁴³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms] [Chem. 12] (In formula (E-2), R ⁴⁴ is an alkanediyl group having 1 to 4 carbon atoms.) (In formula (E-3), R ⁴⁵ and R ⁴⁶ are each independently an alkyl group having 1 to 8 carbon atoms.) [Chem. 14] (In the formula (E-4), R ⁴⁹ is a hydrogen atom or a hydroxyl group. When R ⁴⁹ is a hydrogen atom, R ⁵⁰ is a hydrocarbon group having 1 to 9 carbon atoms. When R ⁴⁹ is a hydroxyl group, R ⁵⁰ is A divalent hydrocarbon group having 1 to 9 carbons or a divalent group having an oxygen atom between the carbon-carbon bonds) [Chem. 15] (In the formula (E-5), R ⁵¹ and R ⁵² are each independently a monovalent hydrocarbon group having 1 to 6 carbon atoms or a monovalent group having an oxygen atom between the carbon-carbon bond)

As specific examples of the specific solvent, for example, the compound represented by the formula (E-1) includes propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ether, and 3-methoxy-1. -Butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethanol monopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ether acetate , Diethylene glycol dimethyl ether, etc .; Examples of the compound represented by the formula (E-2) include cyclobutanone, cyclopentanone, and cyclohexanone; compounds represented by the formula (E-3), such as Examples include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-isobutyl ketone, methyl-n-pentyl ketone, and ethyl- N-butyl ketone, methyl-n-hexyl ketone, di-isobutyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4 -Glutarionone, acetone acetone, diisobutyl ketone, and the like; examples of the compound represented by the formula (E-4) include methanol, ethanol, propanol, butanol, pentanol, and 3-methoxybutane Alcohol, hexanol, heptanol, octanol, furfuryl alcohol, Monools such as phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol, or ethylene glycol, 1,2-propylene glycol, 1,3- Polyols such as butanediol and 2,4-pentanediol; Examples of the compound represented by the formula (E-5) include partial esters of polyols (eg, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether). , Ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Partial esters of polyols such as monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, and dipropylene glycol monopropyl ether), methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, isobutyl acetate, Tributyl ester, 3-methoxybutyl acetate, 2-ethylhexyl acetate, methyl ethyl acetate, ethyl ethyl acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether Acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, dipropylene glycol monomethyl ether acetate, glycol diacetate Methoxyacetate Triethylene glycol, ethyl propionate, n-butyl propionate, di-n-butyl propionate, methyl lactate, ethyl lactate, n-butyl lactate, n-pentyl lactate, diethyl malonate, Dimethyl phthalate and so on. Furthermore, as the specific solvent, one kind may be used alone, or two or more kinds may be used in combination.

The use ratio of the specific solvent is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 50% by mass or more with respect to the total amount of the solvents used in the preparation of the liquid crystal alignment agent. In addition, the upper limit of the proportion of the specific solvent used is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably the total amount of the solvents used in the preparation of the liquid crystal alignment agent. It is 80% by mass or less.

The solid content concentration in the liquid crystal alignment agent (the ratio of the total mass of components other than the solvent of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity and volatility, and is preferably 1% to 10% by mass. % Range. When the solid content concentration is less than 1% by mass, the film thickness of the coating film becomes too small, and it is difficult to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by mass, the film thickness of the coating film becomes too large, and it is difficult to obtain a good liquid crystal alignment film. In addition, the viscosity of the liquid crystal alignment agent tends to increase and the coatability tends to decrease. .

<< Liquid Crystal Alignment Film and Liquid Crystal Element >> The liquid crystal alignment film of the present disclosure is formed of a liquid crystal alignment agent prepared as described above. The liquid crystal element of the present disclosure includes a liquid crystal alignment film formed using the liquid crystal alignment agent described above. The operation mode of the liquid crystal in the liquid crystal element is not particularly limited. For example, it can be applied to TN type, STN type, and VA type (including Vertical Alignment-Multi-domain Vertical Alignment (VA-MVA) type, Vertical Alignment-Patterned Vertical Alignment (VA-PVA) type, etc.), IPS (In-Plane Switching) type, FFS (Fringe Field Switching) type, Optically Compensated Bend (OCB), Various modes such as Polymer Sustained Alignment (PSA). The liquid crystal element can be manufactured by a method including the following steps 1 to 3, for example. In step 1, a substrate is used depending on a required operation mode. Each of the operation modes in steps 2 and 3 is common.

<Step 1: Formation of a coating film> First, a liquid crystal alignment agent is coated on a substrate, and it is preferable to heat the coating surface to form a coating film on the substrate. As the substrate, for example, glass such as float glass and soda glass; polyethylene terephthalate, polybutylene terephthalate, polyether fluorene, polycarbonate, poly (alicyclic olefin), and the like can be used. Plastic transparent substrate. As the transparent conductive film provided on one surface of the substrate, a NESA film (registered trademark of PPG Corporation) containing tin oxide (SnO ₂ ), and indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) can be used. Indium tin oxide (ITO) film. When manufacturing a TN-type, STN-type, or VA-type liquid crystal element, two substrates provided with a patterned transparent conductive film are used. On the other hand, when manufacturing an IPS-type or FFS-type liquid crystal element, a substrate provided with an electrode patterned into a comb-tooth shape and a counter substrate provided with no electrode are used. The application of the liquid crystal alignment agent to the substrate is preferably performed on the electrode formation surface by a lithographic printing method, a flexographic printing method, a spin coating method, a roll coater method, or an inkjet method.

After the application of the liquid crystal alignment agent, for the purpose of preventing dripping of the applied liquid crystal alignment agent, etc., it is preferable to perform preheating (prebaking). The pre-baking temperature is preferably 30 ° C to 200 ° C, and the prebaking time is preferably 0.25 minutes to 10 minutes. Thereafter, a calcination (post-baking) step is performed for the purpose of completely removing the solvent and subjecting the arsenic acid structure present in the polymer to thermal arsonization. The calcination temperature (post-baking temperature) at this time is preferably 80 ° C to 300 ° C, and the post-baking time is preferably 5 minutes to 200 minutes. The film thickness of the film formed in this way is preferably 0.001 μm to 1 μm.

<Step 2: Alignment Process> When manufacturing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal element, the coating film formed in the step 1 is subjected to a process (alignment process) to impart liquid crystal alignment energy. Thereby, the alignment of the liquid crystal molecules can be imparted to the coating film to become a liquid crystal alignment film. Examples of the alignment treatment include a rubbing treatment in which a coating film is rubbed in a certain direction by a roller wound with a cloth containing fibers such as nylon, rayon, cotton, etc., to impart a liquid crystal alignment ability to the coating film; The above coating film is irradiated with light to impart a liquid crystal alignment ability to the coating film. On the other hand, in the case of manufacturing a liquid crystal element of a vertical alignment type, the coating film formed in the step 1 may be directly used as a liquid crystal alignment film, but an alignment treatment may be performed on the coating film.

The light irradiation for light alignment can be performed by a method such as a method of irradiating a coating film after the post-baking step, a method of irradiating a coating film after the pre-baking step and before the post-baking step, A method of irradiating a coating film during heating of the coating film in at least one of a pre-baking step and a post-baking step. As the radiation irradiated to the coating film, for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm can be used. Ultraviolet light including light having a wavelength of 200 nm to 400 nm is preferred. When the radiation is polarized, it may be linearly polarized or partially polarized. When the radiation used is linearly polarized or partially polarized, the irradiation may be performed from a direction perpendicular to the substrate surface, or from an oblique direction, or a combination of these may be used. The irradiation direction in the case of non-polarized radiation is an oblique direction.

Examples of the light source used include low-pressure mercury lamps, high-pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, excimer lasers, and the like. The radiation dose is preferably 400 J / m ² to 50,000 J / m ² , and more preferably 1,000 J / m ² to 20,000 J / m ² . After irradiation with light for imparting alignment energy, for example, water, organic solvents (such as methanol, isopropanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, etc.) can be used. Or the process of cleaning the surface of a board | substrate by this mixture, or the process of heating a board | substrate.

<Step 3: Construction of a liquid crystal cell> Two liquid crystal alignment films are prepared in the above-mentioned manner, and liquid crystal is arranged between the two substrates disposed opposite to each other, thereby manufacturing a liquid crystal cell. When manufacturing a liquid crystal cell, for example, two substrates are arranged to face each other with a gap so that the liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded together with a sealant, and the liquid crystal is injected and filled in A method of sealing the injection hole in a cell gap surrounded by a substrate surface and a sealant; a method using a liquid crystal drip (ODF) method, and the like. As the sealant, for example, an epoxy resin containing a hardener and an alumina ball as a spacer can be used. Examples of the liquid crystal include a nematic liquid crystal and a dish-shaped liquid crystal. Among them, a nematic liquid crystal is preferred. In the PSA mode (including the case where the liquid crystal alignment film contains a polymerizable group-containing compound (low molecule or polymer)), after the liquid crystal cell is constructed, a voltage is applied between the conductive films of a pair of substrates. The liquid crystal cell is irradiated with light in a state.

Then, if necessary, a polarizing plate is bonded to the outer surface of the liquid crystal cell to form a liquid crystal element. Examples of the polarizing plate include a polarizing plate in which a polarizing film called an “H film” is sandwiched by a protective film of cellulose acetate, or a polarizing plate including the H film itself. The “H film” is made of polyvinyl alcohol on one side. Extending the alignment side while absorbing iodine.

The liquid crystal element disclosed herein can be effectively used in various applications, such as clocks, portable game consoles, word processors, notebook personal computers, car navigation systems, camcorders, and personal digital assistants. , PDA), digital cameras, mobile phones, smart phones, various monitors, LCD TVs, information displays and other display devices, or dimming films. In addition, a liquid crystal element formed using the liquid crystal alignment agent of the present disclosure can also be applied to a retardation film. [Example]

Hereinafter, specific examples will be described, but the present invention is not limited to these examples. In this example, the weight average molecular weight Mw, number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the polymer were measured by the following methods. <Weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn)> Mw and Mn were measured by gel permeation chromatography (GPC) under the following conditions. The molecular weight distribution (Mw / Mn) was calculated from the obtained Mw and Mn. Device: "GPC-101" by Showa Denko Corporation GPC tubing: "GPC-KF-801", "GPC-KF-802", "GPC-KF-803" and "GPC-KF-803" manufactured by Shimadzu GLC GPC-KF-804 "combined mobile phase: tetrahydrofuran (THF) column temperature: 40 ° C flow rate: 1.0 mL / min sample concentration: 1.0% by mass sample injection volume: 100 μL detector: differential refractometer standard substance: single Disperse polystyrene

<Synthesis of polymer> [Example 1A] A polymer (P-1) was synthesized according to the following scheme 1. [Chemical 16]

A 1000 ml three-necked flask was charged with 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone, and 10.0 g of triethylamine, at room temperature. mixing. Then, 100 g of deionized water was added dropwise from the dropping funnel for 30 minutes, and then mixed under reflux and reacted at 80 ° C. for 6 hours. After the reaction was completed, the organic layer was taken out, and the organic layer was washed with a 0.2% by weight ammonium nitrate aqueous solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure. An appropriate amount of methyl isobutyl ketone was added to obtain a 50% by mass solution of the polyorganosiloxane (E-1) having an epoxy group. In a 500 ml three-necked flask, 26.69 g (0.3 mol equivalent) of side chain precursor (ca-1), 3.09 g (0.1 mol equivalent) of m-aminobenzoic acid, 2.00 g of tetrabutylammonium bromide, and polyorganosilicon were added. 80 g of a solution of oxane (E-1) and 239 g of methyl isobutyl ketone were stirred at 110 ° C. for 4 hours. After cooling to room temperature, the liquid separation and washing operation was repeated 10 times with distilled water. Thereafter, the organic layer was recovered, and repeatedly concentrated and diluted with NMP by a rotary evaporator to obtain a 15% by mass NMP solution of the polymer (P-1) intermediate. After 0.44 g (0.1 mol equivalent) of trimellitic anhydride was added to 50 g of the intermediate solution, preparation was performed using NMP so that the solid content concentration became 10% by mass, followed by stirring at room temperature for 4 hours. This obtained an NMP solution of the polymer (P-1).

[Example 2A to Example 12A and Comparative Synthesis Example 1 to Comparative Synthesis Example 4] The same as Example 1A, except that the kinds and amounts of the compounds used in the synthesis were shown in Table 1 below. Polymerization was performed to obtain each of polymer (P-2) to polymer (P-12) and polymer (R-1) to polymer (R-4).

[Table 1]

The numerical values in Table 1 indicate the use ratio (mole%) of the number of epoxy groups contained in the carboxylic acid and the carboxylic acid anhydride to the epoxy-containing polyorganosiloxane. The abbreviations of the compounds in Table 1 are as follows. (Side chain precursor [C]) ca-1 to ca-5: Compounds represented by the following formulae (ca-1) to (ca-5) [Chem. 17]

(Amino group-containing carboxylic acid) cb-1: 3-aminobenzoic acid cb-2: 4-aminobenzoic acid (carboxylic anhydride) an-1: trimellitic anhydride an-2: 4-nitro-o-benzene Dicarboxylic anhydride an-3: 4-ethynylphthalic anhydride an-4: maleic anhydride an-5: cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride

[Example 13A] A polymer (P-13) was synthesized according to the following scheme 2. [Chemical 18]

A 1000 ml three-necked flask was charged with 90.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 7.3 g of 3-aminopropyltrimethoxysilane, and 500 methyl isobutyl ketone. g and 10.0 g of triethylamine were mixed at room temperature. Then, 100 g of deionized water was added dropwise from the dropping funnel for 30 minutes, and then mixed under reflux and reacted at 80 ° C. for 6 hours. After the reaction was completed, the organic layer was taken out, and the organic layer was washed with a 0.2 mass% ammonium nitrate aqueous solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure. An appropriate amount of methyl isobutyl ketone was added to obtain a 50% by mass solution of polyorganosiloxane (E-2) having an epoxy group and an amine group. In a 500 ml three-necked flask, 26.69 g (0.3 mol equivalent) of side chain precursor (ca-1), 2.00 g of tetrabutylammonium bromide, 80 g of a solution containing polyorganosiloxane (E-2), and 239 g of isobutyl ketone was stirred at 110 ° C for 4 hours. After cooling to room temperature, the liquid separation and washing operation was repeated 10 times with distilled water. Thereafter, the organic layer was recovered, and repeatedly concentrated and diluted with NMP by a rotary evaporator to obtain a 15% by mass NMP solution of the polymer (P-13) intermediate. After adding 0.45 g (0.1 mol equivalent) of trimellitic anhydride to 50 g of the intermediate solution, preparation was performed using NMP so that the solid content concentration became 10% by mass, followed by stirring at room temperature for 4 hours. This obtained an NMP solution of the polymer (P-13).

[Example 14A] A polymer (P-14) was synthesized according to the following scheme 3. [Chemical 19]

In a 500 ml three-necked flask, 26.69 g (0.3 mol equivalent) of side chain precursor (ca-1), 3.09 g (0.1 mol equivalent) of m-aminobenzoic acid, 2.00 g of tetrabutylammonium bromide, and polyorganosilicon were added. 80 g of a solution of oxane (E-1) and 239 g of methyl isobutyl ketone were stirred at 110 ° C. for 4 hours. After cooling to room temperature, the liquid separation and washing operation was repeated 10 times with distilled water. After that, the organic layer was recovered, and repeatedly concentrated and diluted with NMP by a rotary evaporator to obtain a polyorganosiloxane having an epoxy group and a functional group (this was designated as "Polymer (R-1) ") 15% by mass NMP solution. Next, 0.13 g (0.1 mol equivalent) of magnesium oxide and 0.44 g (0.1 mol equivalent) of m-aminobenzoic acid were added to 50 g of the solution containing the polymer (R-1), and stirred at 80 ° C for 24 hours. After cooling to room temperature, it was poured into water to dissolve magnesium oxide. Next, extraction was performed using a mixed solution of diethylene glycol diethyl ether and cyclohexane, and the liquid was repeatedly separated and washed 10 times with distilled water. Thereafter, the organic layer was recovered, and repeatedly concentrated and diluted with NMP by a rotary evaporator to obtain a 10% by mass NMP solution of the polymer (P-14).

[Synthesis Example 1] 13.8 g (70.0 mmol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as a tetracarboxylic dianhydride, and 2,2'-dimethyl-4 as a diamine 16.3 g (76.9 mmol) of 4'-diaminobiphenyl was dissolved in 170 g of NMP and reacted at 25 ° C for 3 hours to obtain a solution containing 10% by mass of polyamic acid. Then, the polyamidic acid solution was poured into a large amount of excess methanol to precipitate a reaction product. The precipitate was washed with methanol, and dried at 40 ° C. for 15 hours under reduced pressure, thereby obtaining polyamic acid (PAA-1).

[Synthesis example 2] Under nitrogen, 16.0 g (113 mmol) of glycidyl methacrylate and 4.0 g (46.5 mmol) of methacrylic acid were added to a 200 mL two-necked flask as a polymerization monomer. 0.6 g (2.4 mmol) of 2,2'-azobis (2,4-dimethylvaleronitrile) as a starting agent and 2,4-diphenyl-4-methyl-1-pentan as a chain transfer agent 1.0 g (4.2 mmol) of ene and 86.4 g of NMP as a solvent were polymerized at 70 ° C. for 5 hours to obtain a target polymer (referred to as “Polymer (PM-1)”). About the obtained polymer (PM-1), the weight average molecular weight Mw measured by GPC polystyrene conversion was 20,000, and the molecular weight distribution Mw / Mn was 2.1.

[Comparative Synthesis Example 5A] A polymer (PM-2) was synthesized according to the following scheme 4. [Chemical 20]

In a 1000 mL eggplant-type flask with a stirrer, 10.0 g of 3,4-epoxycyclohexyl methyl methacrylate, 20.1 g (1 mol equivalent) of side chain precursor (ca-1), and cyclopentyl 500 g of alkane and 1.64 g of tetrabutylammonium bromide (0.1 mol equivalent) were stirred at 110 ° C for 4 hours. Then, 300 g of cyclohexane and 400 g of cyclopentanone were added to the reaction solution, and the solution was washed with 400 g of distilled water 5 times. Thereafter, the organic layer was gradually concentrated to a content of 50 g by a rotary evaporator, and a white solid precipitated in the middle was recovered by filtration. 23.0 g of a compound (MI-6) was obtained by vacuum-drying the white solid. Next, in a 200 mL two-necked flask under nitrogen, 10.0 g (16.9 mmol) of compound (MI-6) as polymerized monomer, 6.0 g of 3,4-epoxycyclohexyl methyl methacrylate (30.5 mmol) and 4.0 g (46.5 mmol) of methacrylic acid, 2,2'-azobis (2,4-dimethylvaleronitrile) 0.6 g (2.4 mmol) as a radical polymerization initiator, and chain transfer 1.0 g (4.2 mmol) of 2,4-diphenyl-4-methyl-1-pentene as an agent and 86.4 g of NMP as a solvent were polymerized at 70 ° C. for 5 hours to obtain a target polymer (will be It is set to "Polymer (PM-2)"). About the obtained polymer (PM-2), the weight average molecular weight Mw measured by GPC polystyrene conversion was 20,000, and the molecular weight distribution Mw / Mn was 2.0.

<Production and Evaluation of Liquid Crystal Display Element (1)> [Example 1B] 1. Preparation of Liquid Crystal Alignment Agent (AL-1) The polymer (P- 1) NMP and Butyl Cellosolve (BC) as solvents are added to 100 parts by mass, and a solution having a solvent composition of NMP / BC = 50/50 (mass ratio) and a solid content concentration of 4.0% by mass is prepared. The solution was filtered with a filter having a pore size of 1 μm, thereby preparing a liquid crystal alignment agent (AL-1).

2. Production of light vertical liquid crystal display element The prepared liquid crystal alignment agent (AL-1) was coated on a transparent electrode surface of a glass substrate with a transparent electrode including an ITO film using a spinner, and heated at 80 ° C. Pre-bake on the plate for 1 minute. After that, it was heated at 230 ° C. for 1 hour in an oven in which nitrogen was replaced in the warehouse to form a coating film having a film thickness of 0.1 μm. Next, a Hg-Xe lamp and a Glan-Taylor lamp were used to irradiate the surface of the coating film with polarized ultraviolet rays of 1,000 J / m ² including a bright line of 313 nm from a direction inclined by 40 ° from the substrate normal to form a liquid crystal. Alignment film. Repeat the same operation to make a pair (two pieces) of substrates with a liquid crystal alignment film. An epoxy resin adhesive containing alumina balls having a diameter of 3.5 μm was coated on the outer periphery of the surface of the substrate having a liquid crystal alignment film by screen printing, and then the liquid crystal alignment of the pair of substrates was performed. The film was face-to-face, pressure-bonded so that the projection direction of the optical axis of the ultraviolet rays of each substrate on the substrate surface became antiparallel, and the adhesive was thermally cured at 150 ° C for 1 hour. Next, a negative liquid crystal (Merck, MLC-6608) is filled into the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port is sealed with an epoxy-based adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, it was gradually cooled to room temperature after being heated at 130 ° C. Next, the polarizing plates are bonded to the outer surfaces of the substrate at an angle of 45 ° to the projection direction of the optical axis of the liquid crystal alignment film on the substrate surface with their polarization directions orthogonal to each other, thereby manufacturing a liquid crystal display element.

3. Evaluation of Liquid Crystal Orientation For the manufactured liquid crystal display element, an abnormal domain in a change in light and dark when a voltage of 5 V was turned ON / OFF (applied / released) was observed with an optical microscope ( The presence or absence of a domain is evaluated as "A", the case where a part has an abnormal domain is set to "B", and the case where the entire domain has an abnormal domain is set to "C" to evaluate the liquid crystal alignment. As a result, the liquid crystal alignment was "A" in the example.

4. Evaluation of Solvent Resistance of Liquid Crystal Alignment Film After applying a liquid crystal alignment agent (AL-1) on a silicone substrate using a spinner, prebaking at 90 ° C on a hot plate for 2 minutes to form a film thickness 1.0 μm coating film. The obtained coating film was heated on a hot plate at 230 ° C for 30 minutes. After the obtained film was immersed in NMP for 1 minute, it was dried at 100 ° C for 5 minutes. The change rate ΔDnmp of the film thickness before and after immersion was obtained by the following formula (1), and the solvent resistance was evaluated by the change rate ΔDnmp. ΔDnmp = [((film thickness before immersion)-(film thickness after immersion)) / (film thickness before immersion)] × 100 ··· (1) The evaluation is that the change rate ΔDnmp is -2% or more and 2 If it is less than or equal to%, set it to "A", if it is within the range of -5% or more and less than -2%, or if it is within the range of more than 2% and less than 5%, set it to "B" and if it is more than 5% Or if it is less than -5%, it is set to "C". In the above examples, the solvent resistance "A" was evaluated.

5. Evaluation of voltage holding ratio (VHR) With respect to the manufactured liquid crystal display device, a voltage of 5 V was applied at an application time of 60 microseconds and an interval of 167 milliseconds, and then the voltage was measured from the time when the application was released to 167 milliseconds. Retention rate. As the measuring device, VHR-1 manufactured by Toyo Technology Co., Ltd. was used. At this time, the case where the voltage retention rate is 90% or more is set to "A", the case where 80% or more and less than 90% is set to "B", and the case where 50% or more and less than 80% is set to "B" "C", and set "D" when it is less than 50%. As a result, the voltage holding ratio was evaluated as "B" in the examples.

6. Evaluation of thermal reliability About the manufactured liquid crystal display element, it heated in the oven set at 110 degreeC for 500 hours. The voltage retention ratio before and after heating was measured by the method described above, and the decrease in the voltage retention ratio after heating was evaluated. At this time, the case where the voltage holding ratio drops to 20% or less is referred to as "A", the case where 20% or more and less than 40% is referred to as "B", and the case where 40% or more is referred to as "C". As a result, the thermal reliability was evaluated as "A" in the examples.

7. Evaluation of printability The prepared liquid crystal alignment agent (AL-1) was coated on a transparent electrode including an ITO film using a flat-type liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd.). The transparent electrode surface of the glass substrate was heated on a heating plate at 80 ° C for 1 minute to remove the solvent, and then heated on a heating plate at 200 ° C for 10 minutes, thereby forming a stylus-type film thickness meter (KLA- A coating film having an average film thickness of 800 Å measured by Tencor (manufactured by). The coating film was observed with an optical microscope with a magnification of 20 times, and the presence or absence of uneven printing and pinholes was checked. In the evaluation, a case where all printing unevenness and pinholes were not observed was set to "A", and a case where at least one of printing unevenness and pinholes was partially observed was set to "B", and the whole was observed. The case of at least one of printing unevenness and pinholes is set to "C". As a result, the printability was evaluated as "B" in the examples.

[Example 2B to Example 15B and Comparative Example 1B to Comparative Example 4B and Comparative Example 7B] Except that the blending composition was changed as shown in Table 2 below, the same solid content concentration as in Example 1B was prepared and prepared separately. A liquid crystal alignment agent was obtained. In addition, an optical vertical liquid crystal display device was produced in the same manner as in Example 1B using each liquid crystal alignment agent, and various evaluations were performed using the obtained liquid crystal display device. The results are shown in Table 2 below. In Table 2, the values of the compound [A], other polymers, and additives are shown in Example 1B, Example 8B, Comparative Example 1B, and Comparative Example 2B. The use ratio [mass parts] of 100 parts by mass of the polymer component in total is shown in Examples 2B to 7B, 9B, 10B, 11B to 18B, and Comparative Examples 3B to 7B. A total of 100 parts by mass of a polyamic acid (PAA-1) used in the preparation of the liquid crystal alignment agent is used in a proportion [parts by mass]. The polymer used in the preparation of the liquid crystal alignment agent for each compound is shown in Example 11B (PM-1) A total of 100 parts by mass of the use ratio [parts by mass].

<Production and Evaluation of Liquid Crystal Display Element (2)> [Example 16B] 1. Preparation of Liquid Crystal Alignment Agent (AL-16) The polymer (P- 8) To 10 parts by mass, 100 parts by mass of the polyamino acid (PAA-1) obtained in Synthesis Example 1 as another polymer, and 3-methoxy-1-butanol (MB) as a solvent were added. , NMP and butyl cellosolve (BC), and a solution with a solvent composition of MB / NMP / BC = 30/20/50 (mass ratio) and a solid content concentration of 4.0% by mass. The solution was filtered with a filter having a pore size of 1 μm, thereby preparing a liquid crystal alignment agent (AL-16).

2. Production of light horizontal type liquid crystal display element The prepared liquid crystal alignment agent (AL-16) was coated on a transparent electrode surface of a glass substrate with a transparent electrode including an ITO film using a spinner, and heated at 80 ° C. Pre-bake on the plate for 1 minute. After that, it was heated at 230 ° C. for 1 hour in an oven in which nitrogen was replaced in the warehouse to form a coating film having a film thickness of 0.1 μm. Then, a Hg-Xe lamp and a Glan-Taylor lamp were used to irradiate the surface of the coating film with polarized ultraviolet rays of 1,000 J / m ² including a bright line of 313 nm from a direction inclined by 90 ° from the substrate normal to form a liquid crystal. Alignment film. Repeat the same operation to make a pair (two pieces) of substrates with a liquid crystal alignment film. An epoxy resin adhesive containing alumina balls having a diameter of 3.5 μm was coated on the outer periphery of the surface of the substrate having a liquid crystal alignment film by screen printing, and then the liquid crystal alignment of the pair of substrates was performed. The film was face-to-face, pressure-bonded so that the projection direction of the optical axis of the ultraviolet rays of each substrate on the substrate surface became horizontal, and the adhesive was thermally cured at 150 ° C for 1 hour. Next, a positive type liquid crystal (Merck, MLC-7028-100) is filled into the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port is sealed with an epoxy-based adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, it was gradually cooled to room temperature after being heated at 130 ° C. Next, the polarizing plates are bonded to the outer surfaces of the substrate at an angle of 90 ° to the projection direction of the optical axis of the ultraviolet rays of the liquid crystal alignment film on the substrate surface with their polarization directions orthogonal to each other, thereby manufacturing a liquid crystal display element.

3. Evaluation About the manufactured light horizontal type liquid crystal display element, the liquid crystal alignment, solvent resistance, voltage holding ratio (VHR), thermal reliability, and printability were evaluated in the same manner as in Example 1B. The results are shown in Table 2 below.

[Comparative Example 5B] A liquid crystal alignment agent was obtained by preparing a liquid crystal alignment agent at the same solid content concentration as in Example 16B except that the blending composition was changed as shown in Table 2 below. A light horizontal liquid crystal display device was produced in the same manner as in Example 16B using each liquid crystal alignment agent, and various evaluations were performed in the same manner as in Example 1B using the obtained liquid crystal display element. The results are shown in Table 2 below.

<Production and Evaluation of Liquid Crystal Display Element (3)> [Example 17B] 1. Preparation of the liquid crystal alignment agent (AL-17) was performed in the same manner as in Example 16B except that the formulation composition was changed as shown in Table 2 below. Liquid crystal alignment agent (AL-17) was prepared with the same solid content concentration.

2. Manufacture of PSA type liquid crystal display element The prepared liquid crystal alignment agent (AL-17) was coated on a transparent electrode surface of a glass substrate with a transparent electrode including an ITO film using a rotator, and a heating plate at 80 ° C Pre-bake for 1 minute. After that, it was heated at 230 ° C. for 1 hour in an oven in which nitrogen was replaced in the warehouse to form a coating film having a film thickness of 0.1 μm. Repeat the same operation to make a pair (two pieces) of substrates with a liquid crystal alignment film. An epoxy resin adhesive containing alumina balls having a diameter of 3.5 μm was coated on the outer periphery of the surface of the substrate having a liquid crystal alignment film by screen printing, and then the liquid crystal alignment of the pair of substrates was performed. The film faced, and the adhesive was thermally cured at 150 ° C for 1 hour. Next, a negative liquid crystal (Merck, MLC-6608) is filled into the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port is sealed with an epoxy-based adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, it was gradually cooled to room temperature after being heated at 130 ° C. Next, an AC 10 V with a frequency of 60 Hz was applied between a pair of electrodes, and the liquid crystal was driven. An ultraviolet irradiation device using a metal halide lamp as a light source was used to irradiate ultraviolet rays at an irradiation amount of 100,000 J / m ² . In addition, the said irradiation amount is the value measured using the light quantity meter measured with the wavelength 365 nm reference | standard. Thereafter, the polarizing plates were bonded to the outer surfaces of the substrate at an angle of 45 ° to the projection direction of the optical axis of the ultraviolet rays of the liquid crystal alignment film on the substrate surface with their polarization directions orthogonal to each other, thereby manufacturing a liquid crystal display element.

3. Evaluation About the manufactured PSA type liquid crystal display element, liquid crystal alignment, solvent resistance, voltage retention (VHR), thermal reliability, and printability were evaluated in the same manner as in Example 1B. The results are shown in Table 2 below.

[Example 18B and Comparative Example 6B] A liquid crystal alignment agent was obtained by preparing a liquid crystal alignment agent at the same solid content concentration as in Example 16B except that the blending composition was changed as shown in Table 2 below. A liquid crystal display element was produced in the same manner as in Example 17B using each liquid crystal alignment agent, and various evaluations were performed in the same manner as in Example 1B using the obtained liquid crystal display element. The results are shown in Table 2 below.

[Table 2]

In Table 2, the numerical values of the solvents indicate the blending ratio (mass parts) of each solvent to 100 parts by mass of the total amount of the solvent used in the preparation of the liquid crystal alignment agent. The abbreviation of the solvent is as follows. NMB: N-methyl-2-pyrrolidone BC: butyl cellosolve MB: 3-methoxy-1-butanol CPN: cyclopentanone PGME: propylene glycol monomethyl ether EDM: diethylene glycol methyl ether PGMEA : Propylene glycol monomethyl ether acetate

From the results of the above examples, it can be seen that according to Examples 1B to 18B using the liquid crystal alignment agent containing the silicon-containing compound [A], a liquid crystal display element having excellent reliability against heat can be obtained. In addition, the obtained liquid crystal display element was excellent in liquid crystal alignment and voltage retention in addition to thermal reliability, and the liquid crystal alignment film was also excellent in solvent resistance and printability. On the other hand, compared with the Example, the comparative example 1B-the comparative example 7B which used the liquid crystal aligning agent which does not contain the silicon-containing compound [A] is inferior in thermal reliability. In addition to not only thermal reliability, but also comprehensive observation of solvent resistance, voltage retention, and printability, the balance of the examples was also improved.

The present disclosure is described based on the embodiments, and it is understood that the present disclosure is not limited to the embodiments or structures. The present disclosure also includes various modifications or modifications within an equivalent range. In addition, various combinations or forms, and other combinations or forms including only one element, one or more or less than one, are also included in the scope or the scope of the present disclosure.

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Claims (12)

A liquid crystal alignment agent includes a silicon-containing compound having a cyclic ether group and a functional group B that reacts with the cyclic ether group. The liquid crystal alignment agent according to item 1 of the scope of patent application, wherein the functional group B is a functional group that reacts with a cyclic ether group by heat. The liquid crystal alignment agent according to item 1 or item 2 of the scope of patent application, wherein the silicon-containing compound is a polymer [P] having a siloxane skeleton. The liquid crystal alignment agent according to item 3 of the scope of patent application, wherein the polymer [P] has a photo-alignment group. The liquid crystal alignment agent according to item 3 or 4 of the scope of application for a patent, wherein the polymer [P] has an alignment manifestation site that aligns liquid crystal molecules. The liquid crystal alignment agent according to any one of claims 3 to 5 in the scope of patent application, wherein the polymer [P] has a group containing a carbon-carbon unsaturated bond. The liquid crystal alignment agent according to any one of claims 3 to 6 in the scope of the patent application, which further contains a polymer [Q] different from the polymer [P]. The liquid crystal alignment agent according to item 7 of the scope of patent application, wherein the polymer [Q] is selected from the group consisting of polyamic acid, polyamidate, polyimide, and a monomer having a polymerizable unsaturated bond At least one of the group consisting of polymers. The liquid crystal alignment agent according to any one of claims 1 to 8 in the scope of the patent application, wherein the functional group B is a carboxyl group or a protected carboxyl group. A liquid crystal alignment film is formed by the liquid crystal alignment agent according to any one of the first to ninth claims of the patent application scope. A liquid crystal element includes the liquid crystal alignment film according to item 10 of the scope of patent application. A polyorganosiloxane includes a cyclic ether group and a functional group B that reacts with the cyclic ether group.